Composition of matter and method of making same



Patented Sept. 12, 1944 UNITED; STATES PATENT "OFFICE COMPOSITION or MATTER AND METHOD or MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves,

Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Application August 2, 1943, Serial No. 497,119

9 Claims.

This invention relates to a new chemical product or composition of matter, our present application being a continuation-in-part of our copending application Serial No. 447,152, filed June 15, 1942.

The main object of our invention is to provide a new chemical product or compound that is particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to. provide a practicable method for manufacturing said new chemical product or compound.

Although one of the primary objects of our invention is to provide a new compound or composition of matter that is an efficient demulsifier for crude oil emulsions of the water-in-oil type, the said compound or composition of matter is adapted for use in other arts, as hereinafter indicated. It also may have additional uses in vvarious other fields which have not yet been investi- Gated.

We have discovered that if one oxyalkylates glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which have utility in various arts, and particularly in the demulsification of crude oil. 5

The compounds herein contemplated may be produced in any suitable manner, but are usually manufactured by following one or two general procedures. In one of said procedures glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to ive n a idic material, or intermediate product, which, in turn,

35 in which n" has the value of one or two.

is reacted with an alcoholic body of the kind hereinafter described, and momentarily indicated by the formula R1(OH) m. Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may. vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure isv to react an alcohol of the formula type R1(OH)m with a polybasic acid, so as to produce an intermediate product, and then react said intermediate product or fractional ester with the selected malhlated glycerol. I I

Glycerol may be conveniently indicated by the following formula: I c

If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylate glycerol of the following formula:

( I AO) n' CaHrOx-(CzHnO) I'H in which the value of 11.- may vary-from 3 to 10 and all the values of n need not be identical. If a polybaslc carboxy acid be indicated by the formula:

COOH

Likewise, if three moles of a 'polybasic acid are employed, the compound may be indicated by the following formula: I

. (CzHiO) ,uOO C R(C 0 0H),."

CsHiOr-(CzJLOiIuO 0C R(C O OH) w (CaliiO) O 0 C R(C 0 011),."

If a fractional ester 01' the kind exemplified by the three preceding formulae is reacted with one or more moles of an alcohol 01' the kind .previously ducribed in a generic sense as 31(08)...

then obviously, one may obtain a material of the type indicated by the following formula:

" oxide and glycid, which, although not included,

strictly speaking, by the unitary structure 'CnI'IZnO, is included within the meaning of the hereto appended claims and may be simply considered as a variant of propylene oxide, 1. e., hydroxypropylene oxide. Similarly, where a carboxylio hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radicaL'or by an organic group derivedfrom an alcohol, such as an aliphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an-amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broader scope, as follows: a

in which n replaces the numbers 2, 3 or 4, Z includes the acidic hydrogen atom itself. In the above formula, and hereafter, for convenience, R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperature then the monomeric form is most likely to result. The production of the compounds herein contemplated is the result of oneor more esteriflcation steps. As is well known, esteriflcati'on procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one of several procedures. One procedure is to pass an inert, dried gas through the mass to be esterified, and have present at the same time a small amount of a catalyst, such as dried. HCl gas, a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap resinous in nature.

out the water and return the liquid to the reacting vessel. This procedure is commonly employed in the arts, and for convenience, reference is made to U. S. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulae indicating the compounds under consideration, it'

can be understood that such compounds, in numerous instances, have the property ofpolyfunctionality. Inview of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under II suitable conditions, instead of obtaining the monomeric compounds indicated, one would, in reality, obtain a polymer in the. sense, for example, that polyethylene glycols represent a polymer of ethylene glycol. The term "polymer is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as the monomer. In the present instance, however, polymerization involves the splitting and loss'of water so that the process'is essentially self-esteriflcation. Thus, 1 strictly speaking, the polymeric compounds are not absolutely isomers .of the monomeric .compounds, but since, for all practical purposes, they can be so indicated, and since such practice is common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds.

In view of what has been said, and in view of the recognized hydrophile properties of 'the recurring oxyalkylene. linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are balsam-like and sub-resinous or semi- The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred to as an A resin, or a B resin, as

distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis, Chemistry of Synthetic Resins "(1935), pages 862, et. seq.). 7 Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed which contain neither a free hydroxyl nor a free carboxyl group, and one may also obtain a compound of the type in-which there is present at least one free carboxyl, or at least, one free hydroxyl, or both. The word polar hassometimes been used in the arts in hereto appended claims the word "polar" is used in this specific sense.-

We are aware that compounds similar to those contemplated in the present instance may be derived from polyhydroxylated compounds having more than three hydroxyl groups. For instance,

they may be derived from acylic diglycerol, triglycerol, tetraglycerol, mixed polyglycerols, mannitol, sorbitol, various hexltols, dulcitol, pentaerythritol, sorbittan, mannitan, dipentaerythritol .monoether, and other similar compounds. Such particular types in which higher hydroxylated materials are subjected to oxyaikylation and .droxylated ethylene diamine, etc.

'ethylation, although, as previously pointed out,

then employed'in the same manner as oxyalkylated glycerol is employed in the present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a co-pending application hereinafter referred to. The reactants thus contemplated include the typ in whichthereis an amino or amido nitrogen atom, particularly when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxymethyi) acetamide, th acetamide of tris (hydroxymethyl) aminomethane, tetrahy- Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhat similar class of materials which are described in our application Serial No.

other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals 384,594, filed March 21, 1941, now Patent N0.

2,295,163, dated September 8, 1942. Said patent involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in

the present instance, one, two, orthree, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the 7 price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a subresinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon adaptable, and-also, everything else considered,

the cost is comparatively low on aper molar basis, even though somewhat higher on a per pound basis, Succinic acid or the anhydride has many attractive qualties of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples hereinafter illustrated will refer to the use of maleic anhydride, although it is understood thatany other suitable polybasic acid may be employed. Furthermore,

referenceis made to derivatives obtained by oxy- 75,

have been introduced for each original hydroxyl- Oxrsrrrvurnn GLYCEROL Example 1 184 pounds of glycerol is mixed with /2%, by weight, of'caustic soda solution having a specific gravity of 1.383. The caustic soda acts as a catation of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled,

a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained- This represents 660 pounds of ethylene oxide for 92 pounds of glycerol,

OXYETHYLATED GLYCEROL Example 2 The ratio of ethylene oxide is increased to 18 pound moles for each pound mol of glycerol. Otherwise, the same procedure is followed as in Example 1, preceding.

OXETHYLATED GLYCEROL Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide toglycerol is increased to 21 to one.

OXETHYLATED GLYCEROL MALEATE' Example 1 15 ratio), prepared in the manner previously described, is treated with one pound mole of maleic. anhydride and heated at approximately C.

for approximately thirty minutes to two hours,

with constant stirring, so as to yield a mono-' maleate. I

OXETHYLATED GLYCEROL Manners Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

preceding examples, except that three moles of maleic anhydride are employed so as to obtain the trimaleate.

Oxrzmxmun Gmrcnor. MALIATI Example 4 OXETHYLATED Gnxcnaor. MALEATI Example 5 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to or (1 to 18).

Previous reference has been made to an alcoholic body which has been defined generically by the formula R1(OH) 1n. alcoholic compounds employed as reactants in the manufacture of the present compounds, are fractional esters obtained by reaction between detergent-forming acids and alcohols, and most preferably, detergent-forming acids which are liquid at ordinary temperature, and most especially, unsaturated fatty acids.

Detergent-forming acids are monocarboxy acids having more than 8 and not over 32 carbon atoms, and characterized by the fact that they combine with alkalies such as caustic soda, caustic potash, ammonia, triethanolamine, and the like, to produce soap or soap-like materials. The best examples are, of course, the higher fatty acids, such as oleic acid, stearic acid, palmitic acid, etc. In addition to the higher fatty acids, other well known members of this class include resinic acids, abietic acids, naphthenic acids, and

' acids obtained by the oxidation of petroleum hydrocarbons and commonly referred to as oxidized wax acids.

Generally speaking, the higher fatty acids are apt to contain from 12-14 carbon atoms as a lower limit, to 18-22 carbon atoms as an upper The sub-generic class of As herein used, the term polyhydric alcoho refers to aliphatic alcohols containing two or more hydroxyl groups, and is intended to include such compounds as glycerol, ethylene glycol, beta.-

methyl glycerol, 1,3 propanediol, pentamethylene glycol, alpha, beta, gamma pentaetriol, sorbito], mannitol, and the like, and also the polyhydroxyether alcohols, such as diglycerol', triglycerol, tetra-glycerol, diethylene glycol, etc. Such polyhydric ether alcohols may also be produced by ether formation from two or more different polyhydric alcohols to yield compounds, such as ethylene glycol monoglyceryl ether, 1,3 propanediol monoethylene glycol ether, diethylene glycol monoglyceryl ether, etc. Suitable polyhydroxy ether alcohols may also be produced from a polyhydric alcohol containing three or more hydroxyls and a monohydric alcohol. Examples of such compounds are glycerol monobutyl ether, glycerol monoalkyl ether, pentanetriol monoethyl eth'er, diglycerol monopropyl ether, etc.

COMPLETED MONOMERIC DERIVATIVES Example 1 to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difficulty. In other instances,

however, such high boiling inert vaporizing sol- 1 vent, if employed, might .be permitted to remain limit. Oxodized wax acids may contain as many as 32 carbon atoms. For the sake of brevity, reference will be made to superglycerinated fats, although it is understood that similar products obtained from other detergent-forming acids, as well as fatty acids, are just as acceptable.

Superglycerinated fats can be prepared by a number of well known procedures. One PTO-9 cedure is to react the fatty acid with a suitable polyhydric alcohol. Another procedure is toreact an ester, for instance, a glyceride, with an excess of glycerol. Such procedure is sometimes referred to as re-esterification. Other procedures include the use of ethylene oxide, ethylene chlor hydrin, glycerol monochlorhydrin, glycid, or the like. Since the manufacture of these products is well known, particularly in view of their utility in a number of industries, it does not appear that further comment is required. -However, attention 'is directed to a trade pamphlet entitled "Polyhydric Alcohol Esters, issued by the Glycol Products Company, 1940. This pamphlet describes numerous fractional esters derived from fatty acids which are particularly adaptable for in the reacted mass and appear as a constituent or ingredient of the final product. In any event,

our preference is to conduct the reaction in the absence of any such solvent and permit the reaction to proceed with the elimination of water. The temperature of reaction is about to 200 C. and the time of reaction about 20 hours.

COMPLETED Monoumuc Dmuwrrrv: Example 2 The same procedure is followed as in Completed monomeric derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2" is used instead of the monomaleate.

- COIIIPLETED Monomeric Drmmlrrvz Example 3 The same procedure is followed as in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED Monomcluc DERIVATIVE Example 4 Coxrrsrnn Monoluiuc Dsruvxnvs Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of ethylene glycol monoricinoleate, one adds three pound moles of the monoricinoleate for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol (ratio 1 to has been employed as a raw material or primary reactant. In the present instance, a more highly oxyethylated glycerol is employed, to wit, one involving the ratio of 1 to 18. (See Oxyethylated glycerol maleate, Example 4, preceding.)

COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one having an even higher degree of oxyethylation. For example, one indicated by the ratio of 1 to 21. (See Oxyethylated glycerol maleate, Example 5, preceding.)

COMPLETED MONOMERIC DERrvATIvE Example 8 Mono-olein is substituted for ethylene glycol monoricinoleate, in Examples 1 to 7, preceding.

COMPLETED MONOMERIC DERIVATIVE Example 9 Diethylene glycol monoricinoleate is substituted forethylene glycol monoricinoleate, in Examples 1 to 7, preceding.

COMPLETED MONOMERIC DERIVATIVE Example 10 Propylene glycol monoricinoleate is substituted for ethylene glycol monoricinoleate, in Examples 1 to '7, preceding. 7

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boling point of water and below the pyrolytic point of the reactants.

The products are mixed. and stirred constantly Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as malelc anhydride, and a glycol. water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry off the water formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well known procedure and requires no further elaboration.

However, if

In the previous monomeric examples there is a definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of' this kind, and as is well known, organic reactions per so are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product.

This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsification, one is better off to obtain a polymer in the sense previously described, particularly a polymer whose molecular weight is a rather sinall multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus in instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol,

be removed before subsequent reaction. This, of course, can be done in any simple manner by conversion to sodium chloride, sodium sulfate, or any suitable procedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10,. inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the eflectiveness ,of the low multiple polymers as demulsifiers.

Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents, including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously, the reverse is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials'as' ricinoleic acid to oleic acid, including alcohol acids, such as hydroxy acetic acid, lactic acid, ricinoleic acid and also polybasic acids of the kind herein contemplated.

both the polymers and esterification monomers,

separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in th hereto appended claims.

Although the products ,herein contemplated vary so broadly in their characteristics, 1.1a, monomers through' sub-resinous polymers, soluble products, water-emulsifiable oils or compounds,'hydrotropic materials, balsams, subre'sinousmaterials, semi-resinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of the glycerol used as the raw material. When our newproduct is used as a demulsifier in the resolution of oil field emulsions, the demulsifler may be added to the emulsion at the ratio of 1 part in 10,000, one part in 20,000, one part in 30,000 or for that matter, one part in 40,000. In

' such'ratios it well may be that one can not differerty running through the entire series, notwithstanding variation in molecular size and physical make-up, is absolutely apparent. Such statement is an obvious oversimpliflcation, and does not even consider the resistance of an interiacial layer to crumbling, displacement, being forced into solution, altered wetability, and the like. As to amidiiication polymers, for instance, where Z is a polyaminoamide radical, see what is said subsequently.

1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED Cooanzns Example 1 A material of the kind described previously under the heading Completed nomomeric derivative, Example 3, is heated at a temperature of approximately 220-240" C., with constant stirring, for a period of two to 60 hours, so as to eliminatesufilcient water, in order to insure that the resultant product has a molecular weight approximately twice that of the initial raw material.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is ample 3, and in Completed monmeric derivative,

Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result of continued, using either a somewhat longer reaction time, or it may be, a somewhat higher temperature, or both, so as to obtain a material having a molecular weight of approximately three to four times that of the initial product.

Couraaran PoLnmnrc Drmrvyrrvas Incmnmc HEAT-REARRANGED C'oczunas Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that one employs reactants derived from more highly oxyethylated glycerol, or from oxyethylated ethylene glycol monoricinoleate, or from an intermediate lnvolv ing both such reactants as raw materials.

' COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGBD Coommnns Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of'materials of the kind dea two-step procedure. not convert the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may take place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 200 C. for polymerization. Thus, one pound mole of oxyethylated glycerol maleateof the kind described, ratio 1 to 15 up to 1 to 21, is mixed with three moles of ethylene glycol monoricinoleate, and reacted for twenty hours at approximately 200, until the mass is homogeneous. It is stirred constantly during the reaction. Polyfunctionality may reside in dehydration (etherization) of two hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step, i

illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contemplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or lesser degree, suflicient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. the thinner liquid material isfa monomer and the more viscous-or resinous material is a polymer, as previously described. Such product can be used for demulsiflcation by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

scribed in Completed monomeric derivative, Ex- 1 trade wastes and the like: as germicides, insecticides, emulsifiers for cosmetics, spray-oils, water-- repellent textile finish, etc. These uses are by. no means exhaustive.

However, the most important phase of the pres ent invention, as far as industrial application goes, is concerned with the use of the materials previously described as demulsiflers for water-in- In other words, one need I In many instances it will be found that glass-lined vessel.

. oil emulsions, and more specifically, emulsions of water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents herein described may also be used for other purposes, for instance, as a break inducer in doctor treatment of the kind intended to sweeten gasoline. No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are effective as surface tension depressants or wetting agents in the flooding of exhausted oil-bearing strata. I

As'to using compounds of the kind herein de-' scribed as flooding agents for recovering oil from (See U. S. Patent subterranean strata, reference is made to the herein described as demulsifiers, or in particular.

as surface tension depressants in combination with mineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent. No.

2,233,383, dated February 25, 1941, to De Groote and Keiser. Cognizance'must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction .vessel, speeds up reaction and polymerization, compared with a As has been previously indicated, the subgenus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 497,118, 497,120, 497,121, 497,-' 122, 497,123, 497,124, 497,125, 497,126, 497,127, 497,128, 497,129, 497,130, 497,131, 497,132, 497,133, 497,134 and 497,135 filed August 2, 1943.

Having 'thus described our invention, what we claim anddesire to secure by Letters Patent is:'

1. An ester, being a member of the class consisting'of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat rearranged derivatives thereof, and of the following in which Ris the carboxyl-free radical of a polycarboxy acid having not over 8 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part (a) a polyhydric alcohol radical having at least two carbon atoms and not more than 12 carbon atoms; and (b) a detergent-forming, monocarboxy radical having 8 and not more than 32 carbon atoms; Z is an acidic lwdrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the numerals 1 to 2; :n represents the numerals 0 to 2; y represents the numerals 0 to 2; 2 represents the numerals 1 to 3; :1," represents the numerals 0.to 1; and y represents the numerals 1 to 2.

2. An ester, being a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the followin formula: 9

Ha.O).'00CRC00Z],

. CJHBOP'KCMHMCDR'HIV [(CnH|0)n'00GRCOOR1]. in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part (a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part (a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) a detergent-forming monocarboxy radical having at least 8 carbon atoms, and not more than v 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 'n represents the numerals 3 to 10; a: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals l to 3.

4. An ester, being a polar member of the class consisting of monomers, sub-resinous esterification polymers, and'cogeneric sub-resinous heatrearranged derivatives thereof, and of the following formula:

[(CIH40),.'OOCRCOOZ],

in which R is a carboxyl free radical of a dicarboxy'acidhaving not over 6 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) a detergent-forming monocarboxy radical having at least 8 carbon atoms and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11. represents the numerals 3 to 10; a: rep- 9 resents the numerals 0 to 2; 11 represents the numerals 0 to 2; and z represents the numerals 1 5. 'An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esteriin which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon-atoms; R1 is a water-insoluble hydroxylated fractional -ester radical having as an integral part (a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) a detergent-forming monocarboxy radical having at least 8 carbon atoms and not more than 32 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; a: represents the numerals to 2; y represents the numerals 0 to 2; and z represents the numerals 1 to 3.

. 6. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogeneric sub-resinous heat-rearranged derivatives thereof, and of the following formula: I

[(c,H40).'00 CRCO oz CiHsOr-KCiHiO) I'Hl" [(oH40 ,.'oo CR0 0 0a,

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as anintegral part (a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) a higher fatty acid radical having at least 8 and not more than 18 carbon atoms; Z is an acidic-hydrogen atom equivalent including the acidic hydrogen atom itself; 11 represents the numerals 3 to :6 represents the numerals 0 to in which R is a carboxyl-free radical of a dicarboxy acid having not over '6 carbon atoms;

R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part (a) a polyhydric alcoholradical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) an unsaturated higher, fatty acid radical having at least 8 and not more than 18 carbon atoms; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; 0: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals l to 3.

8. An ester, being a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogenericsub-resinous heat-rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having not over 6 carbon atoms; R1 is a water-insoluble hydroxylated fractional ester radical having as an integral part (a) a polyhydric alcohol radical having at least 2 carbon atoms and not more than 12 carbon atoms; and (b) a ricinoleic acid radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogenation itself; n represents the numerals 3 to 10; x represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

9. A method for manufacturing esters as de.- fined in claim 1, consisting of. reacting an oxy- 'alkylated glycerol with a polycarboxy acid having not over 8 carbon atoms, and subsequently reacting said intermediate product with a waterinsoluble hydroxylated ester having as an integral part (a) a polyhydric alcohol radical having at least 2 and not more than 12 carbon atoms; and (b) a detergent-forming monocarboxy radical having at least 8 carbon atoms and not more than 32 carbon atoms.

MELVIN DE GROOTE. BERNHARD KEISER. 

